The nature of the accumulation patterns within the lichen is assessed in terms of metal localization within the different thallus components (i.e. rhizinae, thallus without rhizinae, phycobiont, mycobiont) and the importance of substrate concentrations in controlling localization. Peltigera canina, P. polydactyla, P. rufescens, Cladonia furcata, C. impexa and C. uncialis from a wide range of natural and man-influenced sites in the British Isles were analyzed for Cr, Cu, Fe, Mn, Ni, Pb and Zn; Cladonia spp. were used for comparative purposes. Metal accumulation capacity (μg g−1) of the rhizinae was maximum for Fe, Mn and Pb. However, the phycobiont was found to have maximal accumulation capacity for Cu, Ni and Zn. The metal accumulation capacities by rhizinae and thallus without rhizinae as well as phycobiont and mycobiont without rhizinae were found to be interrelated and were dependent upon the biologically-available metal concentrations in their associated soils as well as the type of substrate. The total amounts (g) of metals localized within the different thallial components, from two major types of environment (i.e. with background and enhanced metal concentrations), are presented; rhizinae accumulate the highest concentrations of all metals under enhanced environments.